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Host-Guest Interactions between Calixarenes and Cp(2)NbCl(2).

Alexis Morales1, Alberto Santana, Gerhard Althoff

  • 1Department of Chemistry, University of Puerto Rico, Mayagüez, PR 00681.

Journal of Organometallic Chemistry
|June 29, 2011
PubMed
Summary

Niobocene dichloride (Cp(2)NbCl(2)) forms inclusion complexes with p-sulfonic calix[6]arene in the solid state. This host-guest interaction was confirmed using various spectroscopic and computational methods, highlighting the role of sulfonate groups.

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Area of Science:

  • Supramolecular Chemistry
  • Organometallic Chemistry
  • Materials Science

Background:

  • Calixarenes are versatile host molecules with tunable properties.
  • Niobocene dichloride (Cp(2)NbCl(2)) is an organometallic compound with potential applications.
  • Investigating host-guest interactions is crucial for developing new materials and separation techniques.

Purpose of the Study:

  • To investigate the formation of inclusion complexes between niobocene dichloride and calixarene hosts.
  • To elucidate the structural and chemical aspects of these host-guest interactions.
  • To determine the influence of calixarene functionalization on complexation.

Main Methods:

  • Solid-state and solution Nuclear Magnetic Resonance (NMR) spectroscopy ((1)H, (13)C CP MAS).
  • Ab-initio computational calculations.
  • Thermogravimetric analysis (TGA).
  • Fourier-transform infrared (FTIR) and Raman spectroscopy.
  • Powder X-ray Diffraction (PXRD).

Main Results:

  • The formation of a true inclusion complex between Cp(2)NbCl(2) and p-sulfonic calix[6]arene in the solid state was confirmed.
  • Ab-initio calculations and NMR data indicated that Cp(2)NbCl(2) is encapsulated within the p-sulfonic calix[6]arene cavity.
  • Raman spectroscopy suggested potential coordination between Nb(V) and the sulfonate oxygen atoms, although hydrolysis of Cp(2)NbCl(2) was noted.
  • In contrast, no inclusion complex was observed in CDCl(3) solution with non-sulfonated calix[6]arene, indicating the importance of sulfonate groups for complexation.

Conclusions:

  • P-sulfonic calix[6]arene effectively forms solid-state inclusion complexes with niobocene dichloride.
  • The sulfonate groups play a critical role in mediating the host-guest interaction and facilitating inclusion.
  • The absence of complexation in solution with non-sulfonated calix[6]arene underscores the significance of specific functional groups in host-guest chemistry.